New detergent composition

ABSTRACT

A new detergent composition comprising at least one of surface active agents represented by the general formula (I), its organic amine salts, ammonium salts, alkali metal salts and non-alkali metal salts, or their acid complex salts, and/or an amphoteric surfactant derived from a compound of the general formula (II) by treatment with an amphoterizing agent, its organic amine salts, ammonium salts, alkali metal salts, non-alkali metal salts or their acid complex salts, as an active component:   WHERE A, B, X, Y, R, Z, W, m, n are as defined in the specification. The present surface active agent can be used widely as a detergent either independently or together with any known detergent. The composition exhibits an excellent detergency, bubble formability and bubble durability for laundry, when washed with this composition, and moreover, it can give the laundry an antistatic property, a resistivity to resoiling and a soil releasability of a prolonged duration.

United States Patent [151 Marumo Dec. 17, 1974 [76] Inventor:

[ NEW DETERGENT COMPOSITION Hideo Marumo, 5-4 Nishikubo, 3 Chome, Tokyo,Japan 22 Filed: May 5,1972

21 App]. No.: 250,653

[30] Foreign Application Priority Data May 10, 1971 Japan 46-30391 Jan.26, 1972 Japan 47-9019 [52] US. Cl 252/547, 252/DlG. 7, 252/DIG. 13,252/546, 252/548, 260/534 E [51] Int. Cl. ..C1ld 1/18, Cl 1d 3/26 [58]Field of Search 252/546, 548, 547, DIG. l3, 252/DIG. 7; 260/534 E, 534 M[56] References Cited UNITED STATES PATENTS 3,555,079 l/l97l Marumo etal. ZOO/501.13

Primary Examiner-Leon D. Rosdol Assistant [imminer-Edith L. RollinsAllorncy, Agent, or FirmCushman, Darby & C ushman [57] ABSTRACT A newdetergent composition comprising at least one of surface active agentsrepresented by the'general formula (I), its organic amine salts,ammonium salts,v

alkali metal salts and non-alkali metal salts, or their acid complexsalts, and/or an amphoteric surfactant derived from a compound of thegeneral formula (II) by treatment with an amphoterizing agent, itsorganic amine salts, ammonium salts, alkali metal salts, nonalkali metalsalts or their acid complex salts, as an active component:

N-C-rCOOH ......(1- R R CHY- CH2 NX(CH2) N I m n w.'. (11

8 Claims, N0 Drawings NEW DETERGENT COMPOSITION BACKGROUND OF THEINVENTION a. Field of the Invention This invention relates to a newdetergent composi- I ,tion, and more particularly toa new detergentcompoagents derived from a compound having the general coon (I) whereinA andB represent hydrogen atoms or groups R-CH-Cl-hor (CH CHRO) H,(wherein R is a hydrocarbon group having2 to 28 carbonatoms and R is ahydrogen atom or a group CH' X represents a hydrogen atom or ahydrocarbon group having 6 to 30 carbon atoms, Y represents ahydrogenatom, a group CH -CH CH(CH )CH I -(CH ),,COOH, (wherein n is aninteger from Ho (wherein D and E are hydrogen atoms or groups n-cu-cmor-(CH CHR'O)},H), p and q are integers-from 0 to 50, and when X is ahydrogen atom, at-least one of A; I B, D and E is agroup or when A, Band Y are all hydrogen atoms, X is the. hydrocarbon group'having 2 to 28carbon atoms, or

R CH-CHZ n wherein R represents a hydrocarbon group of 4 to 30 carbonatoms, Z represents a hydrogen atom or a group (CH CHR'O),,H, (whereinR-' is a hydrogen atom or a group --CH and p is an integer from 1 to X,Y, and W represents hydrogen atoms or groups or (CH CHR'O),,H), m is aninteger from 2 to 10, n

is an integer from 0 to 5, and X, Y, Z and W cantake groups differentfrom one another at the same time.

b. Description of the Prior Art Generally, an ionic surface activeagents such as linear alkylbenzenesulfonates, sodium salts of saturatedlinear alcohol sulfates or the like, and non-ionic surface active agentssuch as nonylphenol ethylene oxide adduct or the like, as used inwashing of natural fibers and synthetic fibers. However, when suchdetergents are used, the fibers cleansed with such detergents have adeteriorated hand feel and the antistatic property of thefibers-is-lost. Therefore, it has been the usual practice to give thewashed fibers an additional treatment with a soft-finishing agent or anantistatic agent. However, these properties which are thus added to thefibers disappear when the fibers are washed again. On the other hand,when the fibers are washed with a known detergent mixed with asoft-finishing agent and an antistatic agent, the individual effects ofthese mixed agents are not exhibited clearly, but rather they serve, inmany cases, only to lower the activity of the detergent per se.Therefore, when the soft-finishing agent, antistatic agent or the like,are used, it is necessary to add these agents into a rinsing solutionafter cleansing or to subject the washed fibers to a separate treatmentwith these agents, and thus a great inconvenience is experienced,

Further, detergents prepared from petroleum or alcohol base used as adetergent for food ware or vegetable have an excellent detergency buthave a property to damageskins. Thus, the use of the syntheticdetergents has recently become a great problem. Furthermore, thebiodegradability of a surface active agent blended in the syntheticdetergent for washing, and the pollution by condensed phosphates havebeen recently regarded as the public pollution problems.

SUMMARY OF THE INVENTION novel detergent composition having less skinirritativeness, and moreover a good biodegradability, and further thepresent detergent composition does not re quire so much builders such ascondensed phosphates.

in the prior patent application of the present inventor for a detergentcomposition U.S. Ser. No. 168,413, now U.S. Pat. No. 3,719,613, it wasdisclosed that a water-insoluble metal salt of the amphoteric surfaceactive agent of a long-chain imidazoline type was dis- 7 persed andsolubilized in a water system with an effective dispersant, and theresulting transparent solution was externally deposited and absorbed onthe surfaces of the fibers. As a result of further studies, the presentinventors have found that the similar effect can be attained by thepresent novel compounds.

The novel compounds of the present invention can be used alone as adetergent, or added to the known detergent as an additive to improvedetergency, bubble formability and bubble durability and endow anantistatic property, resistibility to resoiling and soil releasabilityto a material to be washed. The present detergent composition can beregarded as a kind of polymeric electrolytes or polymeric surface activeagent. Therefore; its critical micelle formation concentration is verylow, for example, about one one-hundredth to one onethousandth of thatof alkylbenzenesulfonates. That is,

the present detergent composition can exhibit a good surface activity ata very low concentration and shows a good detergency. Furthermore, astrong monolayer is formed on the surfaces of material to be washedthrough absorption, and can be stably retained on the surface even inthe cleansing step or even after drying. Thus, the antistatic propertyand soil releasability can be endowed thereby to the materials to bewashed for a considerably prolonged period of time. That is to say, thepresent detergent composition can be used alone in the antistatic,anti-redeposition and soil release treatments.

As described above, the feature of the present detergent composition canbe obtained without any failure even if it is added to the otherconventional detergent composition, but particularly when the presentcomposition is added to the conventional carpetshampoo consisting mainlyof sodium alkylsulfates ester, very stable bubbles can be obtained.Furthermore, the carpet surface is not so much wetted as necessary, andthe fouling components can be effectively absorbed onto C1 H21 CH cH2 NHCH-COONa (A) CaCZ;

the bubble interfaces, whereby an excellent carpet surface having a goodantistatic property, good anti-soil property and a good soilreleasability can be obtained.

Moreover, the present amphoteric surface active C H -CH-CH5-NH-CHCOONato household detergent,'industrial detergent, hair shampoo, carpetshampoo, syndet bar, soap, or the like. Furthermore, the present surfaceactive agent can be used as an organic builder for detergents.

On the other hand, the present detergent composition has a wide use asan industrial detergent, for example, various detergents in the fiberindustry, a detergent in the cleaning industry, a metal detergent, anautomobile, ship or vehicle cleaner, or as a cleaner for plant orequipments in the food industry, or cleaner for food itself or as acleaning agent and germicide for food container, or the like.

DETAILED DESCRlPTlON OF THE PREFERRED EMBODlMENTS Now, a process forproducing a novel surface active agent used in the present inventionwill be outlined.

The compound as represented by the general formula (I) is obtained byadding 1,2-epoxyalkane or a-olefin to a natural or synthetic a-aminoacid, or further by reacting ethylene oxide or propylene oxide with theresulting product. For example, a product (A) obtained by reactingdisodium glutamate with 1,2- epoxydodecane in a solvent mixture ofalcohol-water is double-decomposed with calcium chloride to a compound(B):

l I (A) CH CH COONa OH CH CH C'OONa C H -CHCH -NHCH-COO l l Ca (B) OH CHCH COO When 20 moles of ethylene oxide are added to one mole of theproduct (A), a compound (C) is obtained. When the compound (C) isdouble-decomposed with zinc chloride, a compound (D) is obtained:

ca CH 0) H I 2 2 q C I-l -CH-Cl-l-N-CHCOON8.

I CH CH COONa (CH CH O H decorrlposed with the corresponding inorganicmetal salt, for example, magnesium chloride, a compound (E) is obtained.

peroxide ultraviolet irradiation NaOI-I The compound as represented bythe general formula (II) can be obtained, for example, by. reacting 1,2-expoxyalkane with propylene diamine. The present am- 5 photeric surfaceactive agent can be obtained by reacting an amphoterizing agent, forexample, methyl acrylate, with the resulting compound of the generalformula (ll). The resulting compound is further saponified 20 withsodium hydroxide thereby to obtain a sodium salt of the amphotericsurfaceactive agent, as shown below:

NHCOCH3 NHZ c ,H -ccooNa (E) R CHCH NH(CH NH2 CH2 CHCOOCHa I OH R-CHCHNH(CH 3NHCH CH COOCH NaOH RCHCHZNIHCH NHCH CH COONa CHgOH i OH 7 8 Whenethylene oxide or propylene oxide is added to Examples of the amphotericsurface active agents the resulting sodium salt, adduc ts containingvarious having the formula (I) include the following commoles ofethylene oxide or propylene oxide can be obpounds: tained.

'c n CHCH NHCH COO I Ca 1 OH 2 C 1 H2 QCHCHZNHCHZCOO I Na (2) PC 2 5H 53 CHCH ZNHCHCOO l I Ca (3) OH CH 3 2 1 C H CHCH N-CHCOO Mg (4) c H cncnl CH 3 C u, CHCH;.NHCHCOO r l l ZL'L 3) OH CH CH COO "c H CH-CH N-CHCOOl (6) on icn cu coo Ca coca- 'c n cucn nncncoo i OH (CH )r,NHCH- CHC HBa l d on 2 C10 H2 ICHCH 2 NHCHCOO I NH2(CH2CH2OH) 2 (8) OH (CH micoc n2 'c n cucn N cacoo I I OH cri c n Ca (9) coca 2 'C H CHCH NHCHCOO l IOH (CH2)3NHCH2CH-C6H13 NH(CH2CH2OH)3 (10) CeH l I OH (CH NHcocH Ca (ll)cocH 2 Very good c H CHCH NHCH CH NH cacoo 7 I g I j mm) 2 v (55) OH CH2 COO on Oh l l (CH7CHZO) cii cii-cii N'CH' 'CHQ'CH; 'Ni

' 3 I H,o H 2 (56) CH 2 CH 2 0 s 0 CHQCOO CHZC O( CH2CH2 Now, thepresent invention will be explained in de' Table l -Continued tail,referring to Examples. in the Examples, part is by weight.

. Antistatic effect E [Half time of XAMPLE l Compound No. DetergencyHand feel leakage (sec.)] Detergent compositions were prepared each from10 i. with. parts of the present amphoteric' surface active agent, 5 x2W 2% parts of sodium metasilicate, 8 parts of soda ash and 77 29 g gGood parts of Glaubers salt. These detergent compositions 30 Very goodGood were charged each in a standard amount as the heavy 36 y good od3.2 duty detergent (0.165% by weight) into an electric 37 very h h' flld h l' H v I 30 38 was ing mac me i e wit acry 1c i ers onne a 40 verygood Good 44 trademark of acrylic fibers made by Mitsubishi Rayon 44Very good Good 7.6 Co., Ltd., Japan) fouled by wearing, and subjected to46 y good Good washing according to the standard washing procedure. 2;ery good Good 5.0 On the other hand, the acrylic fibers were washedlike- 49 very good Good wise with a commercially available syntheticdetergent 35 50 Very good Good 3.7 and a commercially availablesoft-finishing agent. De- Very 52 Very good Good 2.8 tergency and handfeel of the washed fibers were deter- 53 very good Good 36 minedvisually or by touch. The results are shown in 54 Very good Good 2.9Table 1. It is evident from Table I that the present de- 55 y good- Goodtergent compositions have an excellent detergency, Confirm! very eventhough the present detergent compositions conheavy duty Very good Poor mtain less active components than those of the commer- E ai s on ciallyavailable detergent, and contain no bu lder such. as sodiumtripolyphosphate, etc.

Table 1 EXAMPLE 2 Anlistatic Five parts of the present surfactant wasadded to a Compound No Detergency 5 feel g z z tgf commercial heavy dutydetergent composition consisting, for example, of 25 parts of sodiumlinear alkylben- 2 Very good Good 2- zenesulfonate (LAS), 25 parts ofsodium tripolyphos- 3 3:3 5:83 phate, 5 parts of sodium metasilicate, 5parts of soda 10 v good Good 7 ash and 40 parts of Glaubers salt, whilethe amount of 12 y good 600d 28 LAS was reduced to 20 parts, wherebydetergent com- 13 Very good Good 3.0 14 very good Good 28 positions wereprepared. Fouled polyester sheets were 15 Very good Good 3.5 washedaccording to the standard washing procedure, is 32 using the respectivedetergent composition in a stan- 18 g g Good dard amount as the heavyduty detergent (0.165% by 19 Very good Good 4.7 weight). The results areshown in Table 2. As shown in g? gm 2'? Table 2, the washed shirts had agood hand feel with an v good Good 25 excellent detergency in the caseof the present deter- 23 y good Good gent compositions. Further,cleansing could be carried 24 Ve ood Good 3 5 J; g Goo-d out more easilyby blending the present surfactant in 2 Good 4,0 the detergentcomposition.

Table 2 Table 3 Antistatic efi'ect Static friction- Bubble [Half time ofCompound No. alcoefiicient Hand fecl stability Compound No. DetergencyHand feel leakage (sec.)] 5 12 202 Sofi Good 1 v Good 25 13 0.195 SoftGood 2 2% Good 2.5 14 0200 Soft Good 3 Ve d G 3 0 15 0.193 Soft Good g19 0 199 Soft Good 4 Very good Good 3.5 2 5 Very good Good 5 1 0.210Soft GOOd E 2s 0211 Soft Good 7 Very good Good 3.8 26 0210 Soft G 3.Very good Good 4.0 38 0.194 Soft" Good 9 Very 8 M 46 0204 Soft Good 10y good Good 47 0.210 Soft Good 11 y good Good 4s 0.195 Soft Good 12 ygood Good 49 0.206 Soft Good 13 y good .Good 50 0202 Soft Good 14 Verygood Good 51 0.200 Soft Good 15 y good Good 52 0190 Soft Good 16 .Verygood Good 4.0 53 0.208 Soft Good 17 Very good Good 3.7 54 0.202 SoftGood 18 Very good Good 3.0 55 0.200 I Soft Good 19 Very good Good 4.2 20r so 0198 Soft Good 20 Very good Good 4.0 Commercial 21 Very good Good4.7 shampoo 0230 Ro F ir 22 Very good Good 35 (control) 23 Very goodGood 4.2 24 Very good Good 2.8 25 Very good Good 5.6 32 Very gal 25EXAMPLE 4 ery g Good 53 3:0 m 3% 0.2 parts of the present surfactant wasadded to a carg g Good 5 pet detergent consisting of 0.5 parts of sodiumsalt of 31 Very good Good 4.2 lauryl sulfate, 015 parts of,lauroyldiethanolamide and 3% 5% 30 99.35 parts'of water, while reducingthe amount of the 34 Very good Good 3 7 sodium salt of lauryl sulfate to0.3 parts thereby to pre- 35 y good Good pare carpet detergentcompositions. Fouled beige 36 Very good Good 3.6 37 very good Good 42nylon carpets were washed w th the thus prepared de- 38 Very good 'Good4.3 tergent compositions according to the conventional 39 Very good Good2.8 w 40 veryvgood 4'4 35 carpet ashing procedure comprising bubblmg,brush 4] very Good mg, leaving at a standstill and suction under vacuum.42 Very good Good I 3.7 The results are shown in Table '4. It is obviousthat the 43 Verygmd carpet detergent composition has an improved deter-44 Very good Good 7.8 45 v good Good 5. gency and bubble stab1l1ty andfaster drying by blend- 46 y good Good' 40 ing the present surfactantinto the conventional deter- 47 Very good Good 3.0 1 48 very good Good3.8 gent composition, and an antlstatic property can be en- 49 Very goodGood 2.8 dowed to the icarpets after washing. 50 Very good Good 3L0 5]Very good Good 4.2 Table 4 52 Very good Good 53 Very good Good 45 wemn gof g; xg m gm the c t Antistatic, effect 56 v G 1 Com- Soil right er[Halftime of Co ma] cry g 4 v pound No. releasability washing leakage(sec.)] ggg i g very good Poor m Feeling of ESS, 50 12 Good 3. dry- 0.5

Feeling of dryness, EX 3 l4 GOOd {:zter dry- 0.6 Two percent by weightof the present surfactant was Egg: added to ahair shampoo compositionconsisting, for 15 Good i'asterdry- 1.0 example, of 10 parts of laurylsulfate triethanolamine, g of 2 parts of lauroyldiethanolamide, 8 partsof urea, 3 dryness, parts of sodium salt of lauryl alcohol ether sulfate(3 s?" moles) and 76 parts of water to prepare hair shampoo. 6 geeiing fr e85 Women 5 ha r was washed with the thus prepared hair 18 yg dry 15shampoo according to the conventional procedure. ing The results areshown in Table 3. It is seen that the degeeling'of tergency and bubblestability are improved by blending 20 Good q f a 14 the presentsurfactant to the conventional shampoo gig f composition, and the goodhand feel can be endowed V f g to the hair after washing and drying. 22Good faster dry- 0.3

Table 4-Continued Wetting of the c t right er washing Antistatic effect[Half time of leakage (sec.)]

Com-

Soil pound No. releasability ing Feeling of faster drying Feeling ofess, faster drymg ggerliing of ess, faster dry- 8 Feeling of faster drymg gxeyerlling of faster drying Feeling of faster dry in Feeling ofdryness,

49 faster dry- 1.0

mg Feeling of dryness. faster dry ing Feeling of 555, faster drymgFeeling of ryness, 52 faster drying Feeling of faster drying Feeling ofdryness, faster dryin Fe eling of 55 faster dry- 0.8

ing

Feeling of faster drying Wettish feeling cc 56 Good Commercial carpetsham control Foulings remam EXAMPLE 5 were tested by 10 household wivesfor one month in the winter season (February), and it was found that thedetergent compositions had a very good detergency and gave no irritationto hands, as compared with the controls.

Sodium linear alkylbenzenesulfonate (LAS) 20 parts Amisol CD (a productof Kawakami Fine Chemicals. Co., Japan) 2 parts Urea 6 parts Lanolinalcohol-ethylene oxide (50 moles) adduct 0.2 parts Water 71.8 partsEXAMPLE 6 Glass cleaners having the following composition were prepared,and glass was washed with the thus prepared compositions. In that case,the present surfactants (31), (32) and (33) were used. it was found thatthe compositions had a good detergency, and a lustrous glass surface wasobtained after the washing.

Present surfactant 0.025% by weight Higher alcohol-ethylene oxide (9moles) adduct 0.25 by weight Amisol CD (a product of Kawakami 7 FineChemicals, Co., Japan) 0.50 by weight lsopropyl alcohol 5.0 70 by weightWater 94.225% by weight EXAMPLE 7 Ten parts of the present surfactanthaving the general formula (I) and 3 parts of the present surfactantderived from the compounds having the general formula (ll) were melted,and 87 parts of hot water was added little by little with stirringthereto to dilute the surfactants. The resulting solution was passedthrough a homogenizer at C, and then to the normal temperature, wherebythe detergent composition were obtained. The thus obtained detergentcompositions were subjected to detergency tests in the same method asdescribed in Example 1. The results are shown in Table 5.

The present compositions had a good detergency and endow a good handfeel and antistatic effect.

What is claimed is: v I 1. A detergent composition consistingessentially of at least one surface active agent of the formula:

wherein R is a hydrocarbon of 4 to 30 carbon atoms; Z is hydrogen or--(CH CHR'O),,H,

wherein R is hydrogen or methyl and p is an integer from 1 to 100; X, Yand W are independently hydrogen,

wherein Z and P are as defined above;

m is an integer from 2 to 10;

n is an integer from to and salts thereof.

2. A detergent composition according to claim 1, wherein the surfaceactive agent is amphoterized with an amphoterizing agent ofmonochloroacetic, B-chloropropionic, -y-chlorobutyric andmonochlorosuccinic acids, and their alkali metal salts or esters, maleicanhydride, acrylic or inethacrylic acid esters, and acrylonitrile.

' 3.,The detergent composition according to claim 1 wherein the surfaceactive agent has the formula:

CHZCIHZOII I l0 2l H-CHzN-CH2-CH2N 5 H CHzCOOH CI-IzCI-IzOH CHZCOOH 4.The detergent composition according to claim 1 wherein the surfaceactive agent has the formula:

, wherein the sum of p plus q plus r is, 9.

5. The detergent composition according to claim 1 wherein the surfaceactive agent has the formula 6. The detergent composition according toclaim 1 wherein the surface active agent has the formulaCiuHaaCHCHzNOHzCHzCHzNCHzCH-CrsHaa H cmomooo OH- omomooon .7. Thedetergent composition according to claim 1 wherein the surface activeagent has the formula:

8. A detergent composition comprising the detergent of claim 1 blendedwith atleast one inorganic detergent builder.

1. A DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF AT LEAST ONESURFACE ACTIVE AGENT OF THE FORMULA
 2. A detergent composition accordingto claim 1, wherein the surface active agent is amphoterized with anamphoterizing agent of monochloroacetic, Beta -chloropropionic, gamma-chlorobutyric and monochlorosuccinic acids, and their alkali metalsalts or esters, maleic anhydride, acrylic or methacrylic acid esters,and acrylonitrile.
 3. The detergent composition according to claim 1wherein the surface active agent has the formula:
 4. The detergentcomposition according to claim 1 wherein the surface active agent hasthe formula:
 5. The detergent composition according to claim 1 whereinthe surface active agent has the formula
 6. The detergent compositionaccording to claim 1 wherein the surface active agent has the formula 7.The detergent composition according to claim 1 wherein the surfaceactive agent has the formula:
 8. A detergent composition comprising thedetergent of claim 1 blended with at least one inorganic detergentbuilder.